Aromatic enediyne derivative, organic semiconductor thin film, electronic device and methods of manufacturing the same

ABSTRACT

Disclosed are a novel aromatic enediyne derivative, an organic semiconductor thin film using the same, and an electronic device. Example embodiments pertain to an aromatic enediyne derivative which enables the formation of a chemically and electrically stable and reliable semiconductor thin film using a solution process, e.g., spin coating and/or spin casting, at about room temperature when applied to devices, an organic semiconductor thin film using the same, and an electronic device including the organic semiconductor thin film. A thin film having a relatively large area may be formed through a solution process, therefore simplifying the manufacturing process and decreasing the manufacturing cost. Moreover, it is possible to provide an organic semiconductor that may be effectively applied to various fields including organic thin film transistors, electroluminescent devices, solar cells, and memory.

PRIORITY STATEMENT

This non-provisional application claims priority under U.S.C. §119 toKorean Patent Application No. 2006-0113845, filed on Nov. 17, 2006, inthe Korean Intellectual Property Office, the entire contents of whichare herein incorporated by reference.

BACKGROUND

1. Field

Example embodiments relate to an aromatic enediyne derivative, anorganic semiconductor thin film, an electronic device and methods ofmanufacturing the same. Other example embodiments relate to an aromaticenediyne derivative, an organic semiconductor thin film, which may beprepared from the aromatic enediyne derivative through a solutionprocess, e.g., spin coating and/or spin casting, at about roomtemperature, and has improved chemical and electrical stability andreliability, an electronic device comprising the organic semiconductorthin film and methods of manufacturing the same.

2. Description of the Related Art

In general, flat display devices, e.g., liquid crystal displays and/ororganic electroluminescent displays, are provided with a variety of thinfilm transistors (TFTs) to drive them. The TFT may include a gateelectrode, source/drain electrodes, and a semiconductor layer that isactivated depending on the operation of the gate electrode. The p-typeor n-type semiconductor layer may function as a conductive channelmaterial for controlling the current between the source electrode andthe drain electrode using the applied gate voltage.

As the semiconductor for TFTs, amorphous Si (a-Si) and polycrystallineSi (poly-Si) are mainly used. With the recent trend toward increasedarea, decreased price, and flexibility of displays, research has beendirected toward semiconductors using organic material, in place ofexpensive inorganic material requiring a high-temperature vacuumprocess.

Using low-molecular-weight organic material, e.g., pentacene, as theorganic semiconductor material has been studied. In this regard, thelow-molecular-weight organic material, e.g., pentacene, has beenreported to have increased charge mobility of about 3.2 cm²/Vs˜about 5.0cm²/Vs or more and an improved on/off current ratio, but suffers becausethe low-molecular-weight organic material may require an expensiveapparatus for vacuum deposition upon formation of a thin film and may bedifficult to use to form a fine pattern, and therefore may be unsuitablefor inexpensive preparation of a film having a relatively large area.

Further, as an oligomer-based organic semiconductor, a soluble pentaceneprecursor capable of being annealed at about 120° C.˜about 200° C. andhaving a charge mobility of about 0.1 cm²/Vs has been reported. Inaddition, an oligothiophene precursor, which has charge mobility ofabout 0.03 cm²/Vs˜about 0.05 cm²/Vs and may be annealed at about 180°C.˜about 200° C., has been reported. However, such organicsemiconductors may be chemically unstable during processing forfabrication of a device and are thus difficult to implement in an actualdevice fabrication line. With regard to electrical stability, when thecurrent-electron sweeping is repeated, decreased voltage and decreasedreliability may be undesirably incurred.

Examples of the related art disclose an organic compound having anacetylene group and a method of preparing a thin film through a vacuumdeposition process using such a compound. However, this method mayrequire a vacuum deposition process in order to prepare a thin film, andmay be unsuitable for the inexpensive preparation of a film having arelatively large area, as with pentacene.

SUMMARY

Accordingly, example embodiments have been made keeping in mind theabove problems occurring in the related art, and example embodimentsprovide an aromatic enediyne derivative, which enables the preparationof a chemically and electrically stable and reliable organicsemiconductor through a solution process, e.g., spin coating and/or spincasting, at about room temperature when applied to devices.

Example embodiments provide an organic semiconductor thin filmcomprising the aromatic enediyne derivative, an electronic devicecomprising the organic semiconductor thin film, a method ofmanufacturing an organic semiconductor thin film using the aromaticenediyne derivative and a method of manufacturing an electronic device.The organic semiconductor thin film functions as a carrier transportlayer in the electronic device.

Example embodiments provide an aromatic enediyne derivative representedby any one of Formulas 1 to 3 below:

in Formulas 1 to 3, R₁, R₂, R₃, and R₄ are each independently selectedfrom the group consisting of hydrogen, halogen, a nitro group, an aminogroup, a cyano group, —SiR¹R²R³ (in which R¹, R², and R³ are eachindependently hydrogen or a C₁-C₁₀ alkyl group), a substituted orunsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₂-C₂₀alkenyl group, a substituted or unsubstituted C₂-C₂₀ alkynyl group, asubstituted or unsubstituted C₁-C₂₀ alkoxy group, a substituted orunsubstituted C₆-C₂₀ arylalkyl group, a substituted or unsubstitutedC₆-C₃₀ aryloxy group, a substituted or unsubstituted C₂-C₃₀heteroaryloxy group, a substituted or unsubstituted C₁-C₂₀ heteroalkylgroup, and a substituted or unsubstituted C₂-C₃₀ heteroarylalkyl group,provided that none of R₁, R₂, R₃, and R₄ are hydrogen, X is carbon or aheteroatom, including nitrogen, oxygen, sulfur or selenium (Se), and Aris selected from the group consisting of a substituted or unsubstitutedC₂-C₃₀ fused arylene group and a substituted or unsubstituted C₂-C₃₀fused heteroarylene group, and is condensed with acetylene-substitutedrings on both sides thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

Example embodiments will be more clearly understood from the followingdetailed description taken in conjunction with the accompanyingdrawings. FIGS. 1-3 represent non-limiting, example embodiments asdescribed herein.

FIG. 1 is a graph showing the result of differential scanningcalorimetry (DSC) of the aromatic enediyne derivative synthesized inPreparative Example 1 of example embodiments;

FIG. 2 is a graph showing the result of thermogravimetry analysis (TGA)of the aromatic enediyne derivative synthesized in Preparative Example 1of example embodiments; and

FIG. 3 is a schematic sectional view showing the organic thin filmtransistor (OTFT) of example embodiments.

It should be noted that these Figures are intended to illustrate thegeneral characteristics of methods, structure and/or materials utilizedin certain example embodiments and to supplement the written descriptionprovided below. These drawings are not, however, to scale and may notprecisely reflect the precise structural or performance characteristicsof any given embodiment, and should not be interpreted as defining orlimiting the range of values or properties encompassed by exampleembodiments. In particular, the relative thicknesses and positioning ofmolecules, layers, regions and/or structural elements may be reduced orexaggerated for clarity. The use of similar or identical referencenumbers in the various drawings is intended to indicate the presence ofa similar or identical element or feature.

DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS

Hereinafter, a detailed description will be given of example embodimentswith reference to the appended drawings. In the drawings, thethicknesses and widths of layers are exaggerated for clarity. Exampleembodiments may, however, be embodied in many different forms and shouldnot be construed as limited to the example embodiments set forth herein.Rather, these example embodiments are provided so that this disclosurewill be thorough and complete, and will fully convey the scope ofexample embodiments to those skilled in the art.

It will be understood that when an element or layer is referred to asbeing “on”, “connected to” or “coupled to” another element or layer, itcan be directly on, connected or coupled to the other element or layeror intervening elements or layers may be present. In contrast, when anelement is referred to as being “directly on,” “directly connected to”or “directly coupled to” another element or layer, there are nointervening elements or layers present. Like numbers refer to likeelements throughout. As used herein, the term “and/or” includes any andall combinations of one or more of the associated listed items.

It will be understood that, although the terms first, second, third etc.may be used herein to describe various elements, components, regions,layers and/or sections, these elements, components, regions, layersand/or sections should not be limited by these terms. These terms areonly used to distinguish one element, component, region, layer orsection from another region, layer or section. Thus, a first element,component, region, layer or section discussed below could be termed asecond element, component, region, layer or section without departingfrom the teachings of example embodiments.

Spatially relative terms, such as “beneath,” “below,” “lower,” “above,”“upper” and the like, may be used herein for ease of description todescribe one element or feature's relationship to another element(s) orfeature(s) as illustrated in the figures. It will be understood that thespatially relative terms are intended to encompass differentorientations of the device in use or operation in addition to theorientation depicted in the figures. For example, if the device in thefigures is turned over, elements described as “below” or “beneath” otherelements or features would then be oriented “above” the other elementsor features. Thus, the exemplary term “below” can encompass both anorientation of above and below. The device may be otherwise oriented(rotated 90 degrees or at other orientations) and the spatially relativedescriptors used herein interpreted accordingly.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting of exampleembodiments. As used herein, the singular forms “a,” “an” and “the” areintended to include the plural forms as well, unless the context clearlyindicates otherwise. It will be further understood that the terms“comprises” and/or “comprising,” when used in this specification,specify the presence of stated features, integers, steps, operations,elements, and/or components, but do not preclude the presence oraddition of one or more other features, integers, steps, operations,elements, components, and/or groups thereof.

Example embodiments are described herein with reference tocross-sectional illustrations that are schematic illustrations ofidealized embodiments (and intermediate structures) of exampleembodiments. As such, variations from the shapes of the illustrations asa result, for example, of manufacturing techniques and/or tolerances,are to be expected. Thus, example embodiments should not be construed aslimited to the particular shapes of regions illustrated herein but areto include deviations in shapes that result, for example, frommanufacturing. For example, an implanted region illustrated as arectangle will, typically, have rounded or curved features and/or agradient of implant concentration at its edges rather than a binarychange from implanted to non-implanted region. Likewise, a buried regionformed by implantation may result in some implantation in the regionbetween the buried region and the surface through which the implantationtakes place. Thus, the regions illustrated in the figures are schematicin nature and their shapes are not intended to illustrate the actualshape of a region of a device and are not intended to limit the scope ofexample embodiments.

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which example embodiments belong. Itwill be further understood that terms, such as those defined in commonlyused dictionaries, should be interpreted as having a meaning that isconsistent with their meaning in the context of the relevant art andwill not be interpreted in an idealized or overly formal sense unlessexpressly so defined herein.

According to example embodiments, the aromatic enediyne derivative maybe represented by any one of Formulas 1 to 3 below:

in Formulas 1 to 3, R₁, R₂, R₃, and R₄ are each independently selectedfrom the group consisting of hydrogen, halogen, a nitro group, an aminogroup, a cyano group, —SiR¹R²R³ (in which R¹, R², and R³ are eachindependently hydrogen or a C₁-C₁₀ alkyl group), a substituted orunsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₂-C₂₀alkenyl group, a substituted or unsubstituted C₂-C₂₀ alkynyl group, asubstituted or unsubstituted C₁-C₂₀ alkoxy group, a substituted orunsubstituted C₆-C₂₀ arylalkyl group, a substituted or unsubstitutedC₆-C₃₀ aryloxy group, a substituted or unsubstituted C₂-C₃₀heteroaryloxy group, a substituted or unsubstituted C₁-C₂₀ heteroalkylgroup, and a substituted or unsubstituted C₂-C₃₀ heteroarylalkyl group,provided that none of R₁, R₂, R₃, and R₄ are hydrogen, X is carbon or aheteroatom, including nitrogen, oxygen, sulfur or selenium (Se), and Aris selected from the group consisting of a substituted or unsubstitutedC₂-C₃₀ fused arylene group and a substituted or unsubstituted C₂-C₃₀fused heteroarylene group, and is condensed with acetylene-substitutedrings on both sides thereof.

Further, the substituent of R₁, R₂, R₃, and R₄ may be a halogen atom, ahydroxyl group, a nitro group, a cyano group, an amino group, an amidegroup, or a carboxyl group, and at least one hydrogen atom of Ar in theabove formulas may be substituted with halogen, a nitro group, an aminogroup, a cyano group, —SiR¹R²R³ (where R¹, R², and R³ are eachindependently hydrogen or a C₁-C₁₀ alkyl group), a substituted orunsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₂-C₂₀alkenyl group, a substituted or unsubstituted C₂-C₂₀ alkynyl group, asubstituted or unsubstituted C₁-C₂₀ alkoxy group, a substituted orunsubstituted C₆-C₂₀ arylalkyl group, a substituted or unsubstitutedC₆-C₃₀ aryloxy group, a substituted or unsubstituted C₂-C₃₀heteroaryloxy group, a substituted or unsubstituted C₁-C₂₀ heteroalkylgroup, and a substituted or unsubstituted C₂-C₃₀ heteroarylalkyl group.

A conventional plastic substrate used in the fabrication of flexibledisplays cannot endure a heat-curing temperature of about 150° C. orhigher, thus causing problems related to light weight and flexibility.However, in example embodiments, as low-molecular-weight semiconductormaterial having conjugated chains, the aromatic enediyne derivative maybe used to manufacture an organic semiconductor thin film, therebyenabling the use of a solution process at decreased temperatures,leading to an organic semiconductor thin film having both the regularmolecular arrangement of the low-molecular-weight semiconductor and theelectrical stability of the polymer. The aromatic enediyne derivative ofexample embodiments may be structured in such a way that one acetylenegroup is respectively attached to each end of a double bond of anaromatic substituent thereof in order to form an unsaturated core.Accordingly, the aromatic enediyne derivative may have a specificchemical structure and active mechanism for realizing increasedreactivity, and therefore a radical benzene ring may be easily formedeven at decreased temperatures, thereby achieving polymerization throughintramolecular or intermolecular bonding.

Although Ar of the aromatic enediyne derivative of Formulas 1 to 3 isnot particularly limited, it may be selected from the group representedby Formula 4 below, for example, a thiophene group or a phenyl group maybe useful in order to increase the mobility of a semiconductor. In thearomatic enediyne derivative of Formulas 1 to 3, Ar may be condensedwith acetylene-substituted rings on both sides thereof.

wherein Y is carbon or a heteroatom, including nitrogen, oxygen, sulfuror selenium (Se), and n is about 0 or a positive integer from about 1 toabout 4.

The aromatic enediyne derivative of example embodiments may besynthesized using a conventional process without particular limitation.Such an aromatic enediyne derivative may be used as a material for anorganic semiconductor constituting an active layer and thus may beeffectively applied to the fabrication of various electronic devices,e.g., TFTs, electroluminescent (EL) devices, solar cells, and/or memory.

In addition, example embodiments provide an organic semiconductor thinfilm, manufactured using the aromatic enediyne derivative, and amanufacturing method thereof.

The organic semiconductor thin film of example embodiments may bemanufactured by i) applying a precursor solution, including the aromaticenediyne derivative represented by any one of Formulas 1 to 3 and anorganic solvent, on a substrate to form a coating film and ii) heatingthe coating film for crosslinking thereof.

As such, the precursor solution may be prepared by mixing two or morearomatic enediyne derivatives represented by Formulas 1 to 3. Further,such an aromatic enediyne derivative may be contained in the precursorsolution in an amount of about 0.001 wt %˜about 30 wt %.

The organic solvent used in example embodiments may not be particularlylimited, examples thereof including an aliphatic hydrocarbon solvent,e.g., hexane and/or heptane, an aromatic hydrocarbon solvent, e.g.,toluene, pyridine, quinoline, anisol, mesitylene, xylene and/orchlorobenzene, a ketone-based solvent, e.g., methyl isobutyl ketone,1-methyl-2-pyrrolidinone, cyclohexanone or acetone, an ether-basedsolvent, e.g., tetrahydrofuran and/or isopropyl ether, an acetate-basedsolvent, e.g., ethyl acetate, butyl acetate and/or propyleneglycolmethyl ether acetate, an alcohol-based solvent, e.g., isopropyl alcoholand/or butyl alcohol, an amide-based solvent, e.g., dimethylacetamideand/or dimethylformamide, a halogen-based solvent, e.g., dichloromethaneand/or trichloromethane, a silicon-based solvent, and mixtures thereof.

In this way, when the precursor solution composed of the aromaticenediyne derivative and the organic solvent is prepared, the precursorsolution may be applied on a substrate, thus forming a coating film.

In example embodiments, the substrate for use in the formation of theorganic semiconductor thin film may not be particularly limited as longas it does not inhibit the purpose of example embodiments, examplesthereof including a glass substrate, a silicon wafer, ITO glass, quartz,a silica substrate, an alumina substrate and/or a plastic substrate.

Examples of the process of applying the precursor solution on thesubstrate may include spin coating, dip coating, roll coating, screencoating, spray coating, spin casting, flow coating, screen printing, inkjetting, and drop casting. Among them, spin coating is particularlyuseful in the interest of convenience and uniformity. Where spin coatingis performed, the spin rate may be set in the range from about 100 rpmto about 10,000 rpm.

Subsequently, the resultant coating film may be heated to allow it tocrosslink, thereby obtaining a desired thin film. Such heat treatmentmay be conducted at about 100° C.˜about 250° C., and may be carried outfor about 1 min˜about 100 min at an appropriate temperature within theabove temperature range, or alternatively, may be carried out whilegradually increasing the temperature.

The crosslinking mechanism of the aromatic enediyne derivative may berepresented by Reaction 1 below:

As is apparent from Reaction 1, the acetylene groups attached to thedouble bonds of the aromatic enediyne derivative may be formed intoradical benzene rings at a predetermined or given reaction temperaturedue to the increased reactivity of the active mechanism of enediyne,resulting in a polymer network through intramolecular or intermolecularbonding.

Where a semiconductor thin film is formed using a conventional precursorsolution, the thin film may crack due to the emission of gas created bythe intermolecular bonding or solvent during the heat treatment.However, the organic semiconductor thin film of example embodiments maybe polymerized through the radical reaction using the increasedreactivity of the active mechanism of enediyne, thereby preventing orretarding the thin film from cracking, which may occur due to thegeneration of gas during a continuous process. The crosslinking reactionmay progress without the use of an additive, thus preventing or reducingthe negative effect of interrupting the molecular arrangement due to theuse of the additive, which acts as an impurity.

In addition, example embodiments provide an electronic device,comprising the organic semiconductor thin film as a carrier transportlayer.

The organic semiconductor thin film thus formed may maintain improvedtransistor properties due to intermolecular packing based on the regulararrangement of a monomolecular aromatic enediyne derivative andintermolecular cross-network formation, and may also assure chemical andelectrical stability and reliability upon formation into a polymericthin film. Where the organic semiconductor thin film is applied as thecarrier transport layer to electronic devices, improved properties maybe provided and the cost reduction effect may be maximized or increasedby realizing a solution process at about room temperature.

Specific examples of the electronic device may include OTFTs, ELdevices, solar cells and/or memory. The aromatic enediyne derivative ofexample embodiments may be applied to the above devices using aconventional process known in the art.

A better understanding of example embodiments may be obtained in lightof the following examples which are set forth to illustrate, but are notto be construed to limit example embodiments.

Preparative Example 1 Synthesis of Aromatic Enediyne Derivative

About 1 equivalent of dialdehyde and about 0.5 equivalents of1,6-cyclohexadione were dissolved in ethanol, and about 5% aqueous NaOHwas slowly added thereto. After being allowed to stand overnight, theprecipitate was filtered and dried. About 3 equivalents oftrimethylsilyl acetylene, about 0.1 equivalents of PdCl₂(PPh₃)₂ andabout 0.05 equivalents of CuI were refluxed in THF and diisopropylaminefor about 10 hours, thus obtaining a tetraethynyl compound.

The tetraethynyl compound in THF was slowly added with a Grignardreagent made using about 3 equivalents of trimethylsilyl acetylene, andthen refluxed for about 3 hours. Aqueous SnCl₂ was added to the reactor,and then stirred at about room temperature for about 1 hour. Theresultant organic layer was washed with water and chloroform, dried, andthen purified through silica column chromatography, thus yieldingproduct 1. 1H NMR (300 MHz, CDCl₃) d (ppm) 0.37 (s, 18H), 0.90-0.95 (m,18H), 1.12-1.27 (m, 22H), 1.31-1.38 (m, 8H), 1.67-1.72 (m, 4H), 2.60 (t,4H, J=6.8 Hz), 3.59 (s, 2H), 8.95 (s, 2H), 9.09 (s, 2H)

The product 1 was dissolved in CHCl₃, added with methanol and THF,further added with an excess of about 1N aqueous NaOH, and then allowedto react. The resultant reaction product was washed with water, and theorganic layer was dried and then purified via silica columnchromatography, thus yielding a compound 2. 1H NMR (300 MHz, CDCl₃) d(ppm) 0.88-0.96 (m, 18H), 1.12-1.30 (m, 22H), 1.31-1.40 (m, 8H),1.67-1.72 (m, 4H), 2.61 (t, 4H, J=6.9 Hz), 3.59 (s, 2H), 8.95 (s, 2H),9.17 (s, 2H)

Example 1 Preparation of Organic Semiconductor Thin Film

On a washed plastic substrate, aluminum/niobium (Al/Nb) alloy for a gateelectrode was deposited to about 1000 Å through sputtering, and thenSiO₂ for a gate insulating film was deposited to about 1000 Å using CVD.

Subsequently, Au for source/drain electrodes was deposited to about 1200Å thereon through sputtering. Before being coated with the organicsemiconductor material, the substrate was washed using isopropyl alcoholfor about 10 min and then dried. The sample was dipped into a about 10mM octadecyltrichlorosilane solution in hexane for about 30 sec, washedwith acetone, and then dried. Thereafter, the aromatic enediynederivative of Preparative Example 1 was dissolved to about 0.1 wt % in axylene solvent, applied on the substrate via dropping, and then baked atabout 100° C. for about 30 min in an argon atmosphere, therebyfabricating the bottom-contact-type OTFT as seen in FIG. 3.

Example 2 Fabrication of OTFT

An OTFT was fabricated in the same manner as in Example 1, with theexception that, in the annealing process, the baking was conducted atabout 160° C. for about 30 min.

The DSC of the aromatic enediyne derivative synthesized in PreparativeExample 1 was measured. The results are shown in FIG. 1.

As shown in FIG. 1, the aromatic enediyne derivative of exampleembodiments was found to begin to crosslink at about 150° C. and then toactively react at about 170° C. or lower. As is apparent from theseresults, the aromatic enediyne derivative of example embodiments may beformed into a semiconductor thin film through a low-temperature wetprocess.

Further, the TGA of the aromatic enediyne derivative of PreparativeExample 1 was measured. The results are shown in FIG. 2.

As seen in FIG. 2, the aromatic enediyne derivative of exampleembodiments did not lose any weight up to about 300° C. The aromaticenediyne derivative of example embodiments did not lose weight even at atemperature exceeding the reaction temperature of about 150° C.˜about170° C., which indicates that no more gas was generated from theresultant polymer. Therefore, where the semiconductor thin film wasformed using the aromatic enediyne derivative of example embodiments,the problem of cracking of the thin film attributable to the generationof gas may be prevented or reduced. In addition, this is judged to bebecause triple bonds (C≡C) and hydrogen bond (≡C—H) attached theretoinduced intramolecular or intermolecular bonding in proportion to theincrease in the annealing temperature, such that the benzene ring wasformed and polymerization was realized according to the active mechanismof enediyne when the temperature was increased.

In order to evaluate the electrical properties of the OTFTs fabricatedin Examples 1 and 2, the current transfer properties thereof weremeasured using a semiconductor characterization system (4200-SCS),available from KEITHLEY, and then charge mobility and cut-off leakagecurrent were calculated. The results are given in Table 1 below.

The charge mobility was calculated from the following current equationfor the saturation region using the current transfer curve. That is, thecurrent equation for the saturation region was converted into a graphrelating (I_(SD))^(1/2) and V_(G), and the charge mobility wascalculated from the slope of the converted graph:

$I_{SD} = {\frac{{WC}_{0}}{2L}{\mu\left( {V_{G} - V_{T}} \right)}^{2}}$$\sqrt{I_{SD}} = {\sqrt{\frac{\mu\; C_{0}W}{2L}}\left( {V_{G} - V_{T}} \right)}$${slope} = \sqrt{\frac{\mu\; C_{0}W}{2L}}$${\mu_{FET} = ({slope})^{2}}\frac{2L}{C_{0}W}$

wherein I_(SD) is source-drain current, μ or μ_(FET) is charge mobility,C_(o) is oxide film capacitance, W is the channel width, L is thechannel length, V_(G) is the gate voltage, and V_(T) is the thresholdvoltage.

The cut-off leakage current (I_(off)), which is the current flowing inthe off-state, was determined to be the minimum current in the off-statein the on/off current ratio.

TABLE 1 Charge Mobility Organic Active Layer (cm²/Vs) I_(off) (A) Ex. 1(Annealing at 100° C.) 8 × 10⁻³ 10⁻¹¹ Ex. 2 (Annealing at 160° C.) 6 ×10⁻⁴ 5 × 10⁻¹¹

As is apparent from Table 1, the OTFTs using the aromatic enediynederivative of example embodiments may have decreased off-current ofabout 10⁻¹⁰ A or less while maintaining the performance thereof.Therefore, when applied to various electronic devices, e.g., TFTs, ELdevices, solar cells and/or memory, the aromatic enediyne derivative wasfound to provide an organic semiconductor thin film having improvedelectrical properties.

As described hereinbefore, example embodiments may provide an aromaticenediyne derivative, an organic semiconductor thin film using the same,and an electronic device using the organic semiconductor thin film. Thearomatic enediyne derivative of example embodiments, which is alow-molecular-weight organic semiconductor material having a structure,may be applied using a wet process at about room temperature and may beapplicable to the processing of semiconductors having relatively largearea. A chemically and electrically stable and reliable semiconductorthin film that has a regular molecular arrangement and does not crackmay be provided. The organic semiconductor thin film of exampleembodiments may be effectively used in various fields, including OTFTs,EL devices, solar cells, and memory.

Although example embodiments have been disclosed for illustrativepurposes, those skilled in the art will appreciate that variousmodifications, additions and substitutions are possible, withoutdeparting from the scope and spirit of example embodiments as disclosedin the accompanying claims.

1. An aromatic enediyne derivative, which is represented by any one ofFormulas 1 to 2 below:

in Formulas 1 to 2, R₁, R₂, R₃, and R₄ are each independently selectedfrom the group consisting of hydrogen, halogen, a nitro group, an aminogroup, a cyano group, —SiR¹R²R³ (in which R¹, R², and R³ are eachindependently hydrogen or a C₁-C₁₀ alkyl group), a substituted orunsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₂-C₂₀alkenyl group, a substituted or unsubstituted C₂-C₂₀ alkynyl group, asubstituted or unsubstituted C₁-C₂₀ alkoxy group, a substituted orunsubstituted C₆-C₂₀ arylalkyl group, a substituted or unsubstitutedC₆-C₃₀ aryloxy group, a substituted or unsubstituted C₂-C₃₀heteroaryloxy group, a substituted or unsubstituted C₁-C₂₀ heteroalkylgroup, and a substituted or unsubstituted C₂-C₃₀ heteroarylalkyl group,provided that none of R₁, R₂, R₃, and R₄ are hydrogen, X is carbon or aheteroatom, which is selected from the group consisting of nitrogen,oxygen, sulfur and selenium (Se), and Ar is selected from the groupconsisting of a substituted or unsubstituted C₂-C₃₀ fused arylene groupand a substituted or unsubstituted C₂-C₃₀ fused heteroarylene group, andis condensed with acetylene-substituted rings on both sides thereof. 2.The enediyne derivative as set forth in claim 1, wherein the Ar inFormulas 1 to 2 is selected from a group consisting of Formula 4 below,and is condensed with acetylene-substituted rings on both sides thereof:

wherein Y is carbon or a heteroatom, which is selected from the groupconsisting of nitrogen, oxygen, sulfur and selenium (Se), and n is about0 or a positive integer from about 1 to about
 4. 3. An organicsemiconductor thin film, manufactured using the aromatic enediynederivative of claim
 1. 4. An electronic device, comprising the organicsemiconductor thin film of claim 3 as a carrier transport layer.
 5. Theelectronic device as set forth in claim 4, wherein the electronic deviceis a thin film transistor, an electroluminescent device, a solar cell,or memory.
 6. A method of manufacturing an organic semiconductor thinfilm, comprising: i) applying a precursor solution, including anaromatic enediyne derivative represented by any one of Formula 1 to 2below:

in Formulas 1 to 2, R₁, R₂, R₃, and R₄ are each independently selectedfrom the group consisting of hydrogen, halogen, a nitro group, an aminogroup, a cyano group, —SiR¹R²R³ (in which R¹, R², and R³ are eachindependently hydrogen or a C₁-C₁₀ alkyl group), a substituted orunsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₂-C₂₀alkenyl group, a substituted or unsubstituted C₂-C₂₀ alkynyl group, asubstituted or unsubstituted C₁-C₂₀ alkoxy group, a substituted orunsubstituted C₆-C₂₀ arylalkyl group, a substituted or unsubstitutedC₆-C₃₀ aryloxy group, a substituted or unsubstituted C₂-C₃₀heteroaryloxy group, a substituted or unsubstituted C₁-C₂₀ heteroalkylgroup, and a substituted or unsubstituted C₂-C₃₀ heteroarylalkyl group,provided that none of R₁, R₂, R₃, and R₄ are hydrogen, X is carbon or aheteroatom, which is selected from the group consisting of nitrogen,oxygen, sulfur and selenium (Se), and Ar is selected from the groupconsisting of a substituted or unsubstituted C₂-C₃₀ fused arylene groupand a substituted or unsubstituted C₂-C₃₀ fused heteroarylene group, andis condensed with acetylene-substituted rings on both sides thereof, andan organic solvent, on a substrate to thus form a coating film; and ii)heating the coating film to achieve crosslinking thereof, therebyforming a thin film.
 7. The method as set forth in claim 6, wherein theprecursor solution is prepared by mixing two or more aromatic enediynederivatives represented by Formulas 1 to
 2. 8. The method as set forthin claim 6, wherein the aromatic enediyne derivative is included in theprecursor solution in an amount of about 0.001 wt %˜about 30 wt %. 9.The method as set forth in claim 6, wherein the organic solvent is atleast one selected from the group consisting of an aliphatic hydrocarbonsolvent, which is selected from the group consisting of hexane andheptane, an aromatic hydrocarbon solvent, which is selected from thegroup consisting of toluene, pyridine, quinoline, anisol, mesitylene,xylene and chlorobenzene, a ketone-based solvent, which is selected fromthe group consisting of methyl isobutyl ketone,1-methyl-2-pyrrolidinone, cyclohexanone and acetone, an ether-basedsolvent, which is selected from the group consisting of tetrahydrofuranand isopropyl ether, an acetate-based solvent, which is selected fromthe group consisting of ethyl acetate, butyl acetate and propyleneglycolmethyl ether acetate, an alcohol-based solvent, which is selected fromthe group consisting of isopropyl alcohol and butyl alcohol, anamide-based solvent, which is selected from the group consisting ofdimethylacetamide and dimethylformamide, a halogen-based solvent, whichis selected from the group of dichloromethane and trichloromethane, asilicon-based solvent, and mixtures thereof.
 10. The method as set forthin claim 6, wherein applying the precursor solution is performed usingspin coating, dip coating, roll coating, screen coating, spray coating,spin casting, flow coating, screen printing, ink jetting, or dropcasting.
 11. The method as set forth in claim 6, wherein heating thecoating film is performed at about 100° C.˜about 250° C.
 12. A method ofmanufacturing an electronic device comprising: manufacturing the organicsemiconductor thin film according to claim
 6. 13. The method as setforth in claim 12, wherein the organic semiconductor thin film is acarrier transport layer.
 14. The method as set forth in claim 12,wherein the electronic device is a thin film transistor, anelectroluminescent device, a solar cell, or memory.